CN115073736A - Catalytic method for controllable copolymerization of epoxy and isothiocyanate - Google Patents
Catalytic method for controllable copolymerization of epoxy and isothiocyanate Download PDFInfo
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Abstract
本发明公开了一种环氧与异硫氰酸酯可控共聚的催化方法。本发明利用无金属催化剂首次实现了环氧和异硫氰酸酯化合物的活性可控共聚，合成主链含硫原子的杂链聚合物。在单组分有机碱的催化下，环氧和异硫氰酸酯能够进行严格的交替共聚，生成交替共聚物。使用有机碱和质子酸或Lewis酸构建的双(多)组分催化剂，能够灵活地调控两种单体的相对反应活性，通过一步或一锅两步反应合成序列结构为交替、无规、梯度、锥形、乃至嵌段的杂链共聚物。含活泼氢引发剂能够定量引发聚合反应，因而可对聚合物的分子量、官能度和拓扑结构进行精确的调控。The invention discloses a catalytic method for the controllable copolymerization of epoxy and isothiocyanate. The invention realizes the activity controllable copolymerization of epoxy and isothiocyanate compounds for the first time by using a metal-free catalyst, and synthesizes a heterochain polymer containing sulfur atoms in the main chain. Under the catalysis of one-component organic bases, epoxy and isothiocyanate can undergo strict alternating copolymerization to form alternating copolymers. Two (multi-) component catalysts constructed using organic bases and protonic acids or Lewis acids can flexibly tune the relative reactivity of the two monomers, and the sequence structures are alternate, random, and gradient synthesized by one-step or one-pot two-step reactions. , tapered, and even block heterochain copolymers. Active hydrogen-containing initiators can quantitatively initiate polymerization, thereby enabling precise control of polymer molecular weight, functionality, and topology.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalytic method for controllable copolymerization of epoxy and isothiocyanate.
Background
The copolymer is a polymer containing two or more monomer units, which is formed by two or more monomers jointly participating in polymerization reaction. In contrast to homopolymerization of one monomer, copolymerization of two or more monomers can yield polymers rich in sequence structure, such as alternating, random, gradient, tapered, block, and graft polymers. The sequence structure of the polymer is a decisive influence on the properties of the polymer, so that the copolymerization, in particular the sequence control, isThe polymerization process, as a strategy to enrich the structure and properties of the polymer, has gained vigorous development. The epoxy compound is a basic industrial raw material for synthesizing heterochain macromolecules, can be used for obtaining polyether materials through ring opening homopolymerization, and can also be used for copolymerizing with various polar monomers to obtain copolymer materials with different structures and performances. For example, copolymerization with cyclic esters to obtain degradable polyethers; copolymerizing with anhydride to obtain polyester; and CO 2 /COS/CS 2 Respectively copolymerizing to obtain polycarbonate and polythiocarbonate; and isocyanate to obtain polyurethane. Therefore, the enrichment and development of new epoxy comonomers will greatly expand the variety and properties of polymeric materials. Through full research, the isothiocyanate compound has the advantages of rich structure, wide source, moderate reaction activity and the like, is an ideal monomer for introducing sulfur atoms into a polymer main chain, and is mature to be applied to step-by-step polymerization reaction to generate the polyureaurethane. However, controlled copolymerization of epoxy and isothiocyanate compounds has not been reported. The key point of realizing controllable copolymerization lies in designing and optimizing a proper catalytic system, so that epoxy and isothiocyanate compounds can generate ring-opening reaction and nucleophilic addition reaction, and side reactions such as trimerization of isothiocyanate monomers and dimerization of epoxy monomers and isothiocyanate monomers and the like are fully inhibited or eliminated, and a novel polymer with an accurately controllable sequence structure is obtained.
After the 21 st century, the research on organic small molecular catalysts is in the field of ring-opening homopolymerization and copolymerization of epoxy monomers, and the organic small molecular catalysts show numerous advantages which are comparable to or even superior to those of metal catalysts. The organic base compound is first applied to binary or ternary polymerization of epoxy, cyclic ester and cyclic anhydride monomers to produce copolymer with random, alternate and block sequence structure. Subsequently, the metal-free acid-base combined by the organic base and the protonic acid/Lewis acid brings comprehensive improvement on the reaction rate and selectivity of the catalyst, and further develops carbon dioxide (CO) 2 ) And derivatives thereof, isocyanate and other comonomers, thereby enriching the chemical structure and sequence structure of the copolymer. Therefore, the organic small molecule catalyst has sufficient catalytic activity, excellent chemical selectivity and flexibilityThe controllability is enough to meet the challenge and value of the copolymerization reaction of epoxy and isothiocyanate monomers.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a catalytic method for controllable copolymerization of epoxy and isothiocyanate. The method uses organic base or acid-base pair combined by organic base and protonic acid/Lewis acid as a metal-free catalyst to implement controllable copolymerization of epoxy and isothiocyanate, shows excellent catalytic activity and chemical selectivity, and controllably synthesizes the sulfur-containing heterochain polymer with accurate sequence structure. The reaction can use a plurality of compounds containing active hydrogen as initiators, and further enriches the chemical structure and topological structure of the polymer.
The purpose of the invention is realized by the following technical scheme:
a catalytic method for the controlled copolymerization of epoxy and isothiocyanate comprises the following steps:
under the action of a compound containing active hydrogen as an initiator and an organic base, an acid-base pair formed by the organic base and protonic acid or the organic base and Lewis acid as a catalyst, an Epoxy (EP) compound and an Isothiocyanate (ITC) compound carry out controllable copolymerization reaction to synthesize a heterochain polymer with a main chain containing sulfur atoms.
Preferably, the catalytic process for the controlled copolymerization of epoxy and isothiocyanate comprises the steps of: fully mixing a compound containing active hydrogen and a catalyst, and then adding an Epoxy (EP) compound and an Isothiocyanate (ITC) compound according to a ratio for copolymerization reaction to synthesize a heterochain polymer with a main chain containing sulfur atoms; the catalyst is an acid-base pair combined by organic base, organic base and protonic acid or organic base and Lewis acid.
The Epoxy (EP) and Isothiocyanate (ITC) compounds are copolymerized according to the formula:
preferably, the epoxy compound is at least one of (1) ethylene oxide, (2) linear alkyl ethylene oxide having an alkyl group of 1 to 20 carbon atoms, (3) styrene oxide, (4) cyclohexene oxide, (5) 4-vinylcyclohexane, (6) limonene oxide, (7) linear alkyl glycidyl ether having an alkyl group of 1 to 16 carbon atoms, (8) isopropyl glycidyl ether, (9) tert-butyl glycidyl ether, (10) 2-ethylhexyl glycidyl ether, (11) phenyl glycidyl ether, (12) benzyl glycidyl ether, (13) allyl glycidyl ether, (14) propargyl glycidyl ether, and (15) glycidyl methacrylate. The specific structural formula is as follows:
more preferably, the epoxy compound is at least one of ethylene oxide, propylene oxide and butylene oxide.
Preferably, the isothiocyanate compound is at least one of (1) methyl isothiocyanate, (2) linear alkyl isothiocyanate, in which the linear alkyl group has a carbon atom number of 2 to 20, (3) alicyclic isothiocyanate, in which the alicyclic carbon atom number is 3 to 12, (4) isopropyl isothiocyanate, (5) sec-butyl isothiocyanate, (6) isobutyl isothiocyanate, (7) benzyl isothiocyanate, (8) phenyl isothiocyanate, (9) o/m/p-toluene isothiocyanate, (10) benzoyl isothiocyanate, (11) chloroethyl isothiocyanate, (12) cyclohexyl methyl isothiocyanate, and (13) allyl isothiocyanate. The specific structural formula is as follows:
more preferably, the isothiocyanate compound is at least one of methyl isothiocyanate and phenyl isothiocyanate.
Preferably, the compound containing active hydrogen is at least one of amine, water, alcohol, phenol, carboxylic acid, thiol and amide, and serves to control polymer molecular weight, functionality and topology.
More preferably, the compound containing active hydrogen is at least one of terephthalyl alcohol, benzyl mercaptan, methoxymethyl amine, acetic acid, cis-butene diol and pentaerythritol.
Preferably, the organic base is at least one of a phosphazene base, a triaminophosphine, a tertiary amine, an amidine, and a guanidine; the phosphazene base is BEMP, t BuP 1 、 t BuP 2 、EtP 2 And t BuP 4 at least one of; the triaminophosphine is at least one of HMTP, HETP, TMAP and TIPAP; the tertiary amine is DABCO, PMDETA, ME 6 At least one of TREN and sparteine; the amidine is at least one of DBN and DBU; the guanidine is at least one of TBD, MTBD, TMG and PMG. The specific structural formula is as follows:
more preferably, the organic base is t BuP 1 、 t BuP 2 、 t BuP 4 At least one of DBU and DABCO.
Preferably, the catalyst may be a combination of an organic base with a protic or Lewis acid. The type, proportion and feeding sequence of the organic base and the protonic acid/Lewis acid can influence the relative reactivity of the epoxy and the isothiocyanate, and further control the sequence structure of the generated copolymer, such as an alternating copolymer, a random copolymer, a gradient copolymer, a conical copolymer and a block copolymer.
Preferably, the protonic acid is a (thio) urea-based compound which is 1, 3-diisopropylthiourea, 1, 3-dicyclohexylurea, 1, 3-dicyclohexylthiourea, 1-cyclohexyl-3-phenylurea, 1-cyclohexyl-3- [3, 5-bis (trifluoromethyl) phenyl ] urea, 1-cyclohexyl-3-phenylthiourea, 1-cyclohexyl-3- [3, 5-bis (trifluoromethyl) phenyl ] thiourea, 1, 3-diphenylurea, 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] urea, 1, 3-diphenylthiourea, 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] thiourea and 1- (3-chlorophenyl) -3- [3, at least one of 5-bischlorophenyl ] urea; the Lewis acid is an organic boron compound, and the organic boric acid is at least one of trimethyl borane, triethyl borane, diethyl methoxy borane, triisopropyl borane, tri-n-butyl borane, tri-sec-butyl borane, B-isopinocampheyl-9-boron bicyclo [3.3.1] nonane, triphenyl borane and trifluorophenyl borane. The specific structural formula is as follows:
more preferably, the protonic acid is at least one of 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] thiourea and 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] urea; the Lewis acid is at least one of triethylboron and triphenylboron.
Preferably, the controllable copolymerization reaction can be carried out in the presence or absence of a solvent, wherein the solvent is at least one of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, N-hexane, cyclohexane, acetone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate and gamma-butyrolactone.
Preferably, the temperature of the copolymerization reaction is 15-100 ℃, and the concentration of the isothiocyanate is 2-10 mol/L.
In actual operation, the catalyst dosage and the monomer concentration can be flexibly adjusted, and the time required by the reaction is further controlled. Preferably, the molar ratio of the compound containing active hydrogen, the catalyst, the epoxy compound (EP) and the Isothiocyanate (ITC) compound is (1-10): (0.1-10): (10-1000): (5-1000); when the catalyst is acid-base pair, the molar ratio of the organic base to the protonic acid or Lewis acid is 1: 0.1 to 15; the reaction time is 0.5-200 h.
The invention realizes the controllable copolymerization of epoxy and isothiocyanate by using a metal-free catalyst for the first time, shows higher catalytic activity and excellent reaction controllability, and can obtain a sulfur-containing heterochain polymer with a definite structure.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) under the catalysis of single-component organic base, epoxy and isothiocyanate compound are strictly and alternately copolymerized to avoid epoxy homopolymerization to produce polyether chain segment and to synthesize alternate copolymer.
(2) The combined use of the organic base and the protonic acid or the Lewis acid can effectively weaken or even eliminate side reactions such as trimerization of isothiocyanate, dimerization of epoxy and isothiocyanate and the like, and improve the purity and yield of the copolymer.
(3) The ratio of the organic base to the protonic acid/Lewis acid can obviously regulate and control the copolymerization reaction rate of the epoxy and the isothiocyanate, determine the sequence structure (alternating, random, gradient, conical or block) of the main chain, and influence the mechanical property, the optical property and the thermal stability of the copolymer.
(4) The single-component and double-component metal-free catalysts are various in types, particularly the double-component catalyst can flexibly adjust and optimize catalytic activity, selectivity and a copolymerization method aiming at different monomer combinations and target polymer structures through the combination, proportion and change of a charging sequence of various organic bases and protons/Lewis acids.
(5) The sulfur-containing heterochain polymer synthesized by the metal-free catalyst can effectively avoid the problems of metal poisoning, difficult post-treatment and the like of the catalyst, and has natural advantages when being applied to the fields of biomedicine and electronic appliances.
(6) The copolymerization reaction can use a plurality of compounds containing active hydrogen as initiators to prepare the sulfur-containing polymers with terminal group functionalized, block, multiblock, star, dendritic, hyperbranched and other topological structures.
(7) The epoxy and isothiocyanate compounds available for the copolymerization reaction have varied substituents, and can introduce abundant side group functional groups for the sulfur-containing heterochain polymer. The activity characteristics of anionic polymerization combined with the activity difference of the comonomers promote that the activity controllable copolymerization can be carried out when more than two comonomers are directly mixed or continuously and gradually added, so as to synthesize the heterochain polymer with specific molecular weight and sequence structure. The method simplifies the synthesis process of the functionalized polymer, improves the production efficiency and enriches the product types.
(8) The copolymerization reaction can be carried out under the conditions of no solvent or less solvent and lower catalyst dosage, and has the advantages of atom economy and price. The copolymerization reaction has a wide operation temperature range, greatly improves the simplicity, flexibility and safety of operation, and is suitable for industrial production.
Drawings
FIG. 1 is a schematic representation of phenyl isothiocyanate 1 H NMR chart.
FIG. 2a is a SEC diagram of the copolymer obtained in example 6.
FIG. 2b is a drawing showing the preparation of the copolymer obtained in example 6 1 H NMR chart.
FIG. 3a is a SEC diagram of the copolymer obtained in example 7.
FIG. 3b is a drawing showing the preparation of the copolymer obtained in example 7 1 H NMR chart.
FIG. 4a is a SEC chart of the copolymer obtained in example 9.
FIG. 4b is a drawing showing the preparation of the copolymer obtained in example 9 1 H NMR chart.
FIG. 5a is a SEC chart of the copolymer obtained in example 12.
FIG. 5b shows a copolymer obtained in example 12 1 H NMR chart.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The conversions and copolymer structural characteristics of the epoxy monomers and isothiocyanates in the following examples were measured by Bruker AV400 liquid NMR spectrometer with deuterated chloroform or deuterated dimethyl sulfoxide as the solvent. The relative molecular weight and molecular weight distribution of the copolymer are measured by a volume exclusion chromatograph of 1260Infinity model of Agilent (America), the mobile phase is tetrahydrofuran, the column temperature is 35 ℃, and the flow rate is 1 mL/min; calibration curves were prepared using a series of polystyrene or polyethylene oxide standards.
The parts described in the formulations in the examples below are all molar parts.
Example 1
In this example, a copolymerization reaction of ethylene oxide and methyl isothiocyanate was carried out using terephthalyl alcohol as an initiator and a two-component catalyst of phosphazene base and lewis acid in combination, and the specific operations were as follows:
the ethylene oxide and Tetrahydrofuran (THF) are both used after purification and water removal. Methyl isothiocyanate was purified by distillation and used. In an inert atmosphere, 1 part of terephthalyl alcohol and 1 part of phosphazene base t BuP 1 And a tetrahydrofuran solution (concentration: 1mol/L) containing 0.3 part of triethylboron were charged into a glass reactor dried at 200 ℃ and returned to room temperature, and dissolved by adding tetrahydrofuran. Continuously adding 200 parts of methyl isothiocyanate and 200 parts of ethylene oxide, sealing the glass reaction vessel, uniformly mixing by using a magnetic stirrer, and reacting for 8 hours at room temperature (20-25 ℃). In this example, the monomer concentration of methyl isothiocyanate was 6mol/L, and the product obtained after the polymerization reaction was a colorless viscous liquid. The crude product was decanted from the glass reactor, precipitated in methanol and the catalyst was removed. The polymer was collected and dried in a vacuum oven heated to 80 ℃ for 12h for structural testing.
1 H NMR tests show that the polymer is initiated by terephthalyl alcohol, and only segments of ethylene oxide alternating with methyl isothiocyanate exist, with a strictly alternating sequence structure. In addition to this, the present invention is, 1 chemical shift signals such as polyether and polyisothiocyanate are not observed in an H NMR spectrogram, and the results show that homopolymerization of ethylene oxide, trimerization of methyl isothiocyanate and cyclization reaction of the ethylene oxide and the methyl isothiocyanate are sufficiently inhibited. During the reaction, sampling was performed at equal time intervals. It can be found that the conversion rates of methyl isothiocyanate and ethylene oxide are approximately equal, and the alternating copolymerization reaction characteristics are met. Sampling for 8h gave a methyl isothiocyanate conversion of 100% and a theoretical number average molecular weight of 23.5 kg/mol. The number average molecular weight as determined by SEC was 24.0kg/mol, with a molecular weight distribution of 1.08.
Phosphazene base used in this example t BuP 1 Can not catalyze the copolymerization reaction of the ethylene oxide and the methyl isothiocyanate independently, which shows that t BuP 1 Is weak and is not enough to catalyze the ring-opening reaction of the ethylene oxide. And with triethylboron and t BuP 1 the formed bi-component catalyst can efficiently carry out ring-opening polymerization of ethylene oxide and methyl isothiocyanate at room temperature to obtain a copolymerization product with controllable molecular weight and narrow molecular weight distribution. The resulting polymer structure is shown below:
example 2
In this example, the copolymerization of propylene oxide and phenyl isothiocyanate was carried out using benzyl mercaptan as initiator and a two-component catalyst of phosphazene base and lewis acid, and the specific operations are as follows:
both propylene oxide and Tetrahydrofuran (THF) were used after purification and water removal. The phenyl isothiocyanate was purified by distillation and used. 1 part of phenylmercaptan, 0.08 part of phosphazene base t BuP 2 And a tetrahydrofuran solution (concentration: 1mol/L) containing 0.01 part of triethylboron were charged into a glass reactor dried at 200 ℃ and returned to room temperature, and dissolved by adding tetrahydrofuran. And continuously adding 30 parts of phenyl isothiocyanate and 30 parts of epoxypropane, sealing the glass reaction container, uniformly mixing by using a magnetic stirrer, and reacting for 48 hours at room temperature (20-25 ℃). In this example, the monomer concentration of phenylisothiocyanate was 2.5mol/L, and after completion of the polymerization, the colorless viscous product was poured from the glass reaction vessel to a large amount of methanol to precipitate. The polymer was collected and dried in a vacuum oven heated to 80 ℃ for 12h for structural testing.
1 H NMR measurements showed that the conversion of phenylisothiocyanate was 100% with a theoretical number average molecular weight of 5.9kg/mol, combined with end group analysis to give an actual number average molecular weight of 6.7 kg/mol. The number-average molecular weight determined by SEC was 7.4kg/mol, with a molecular weight distribution of 1.07. The polymer structure is shown below:
example 3
In this example, the copolymerization of butylene oxide and phenyl isothiocyanate was carried out using methoxymethylamine as the initiator and a two-component catalyst combining phosphazene base and lewis acid, and the specific operations were as follows:
butylene oxide and Tetrahydrofuran (THF) are both used after purification and water removal. The phenyl isothiocyanate was purified by distillation and used. In an inert atmosphere, 1 part of methoxymethylamine and 1 part of phosphazene base t BuP 2 And a tetrahydrofuran solution (concentration: 1mol/L) containing 0.3 part of triethylboron were charged into a glass reactor dried at 200 ℃ and returned to room temperature, and dissolved by adding tetrahydrofuran. And continuously adding 300 parts of phenyl isothiocyanate and 400 parts of epoxy butane, sealing the glass reaction container, uniformly mixing by using a magnetic stirrer, and reacting for 96 hours at room temperature (20-25 ℃). In this example, the monomer concentration of phenylisothiocyanate was 3mol/L, and after completion of the polymerization, the colorless viscous product was poured from the glass reaction vessel into a large amount of methanol to precipitate. The polymer was collected and dried in a vacuum oven heated to 80 ℃ for 12h for structural testing.
1 H NMR measurement showed that the conversion of phenylisothiocyanate was 92% and the theoretical number average molecular weight was 57.3 kg/mol. The number-average molecular weight determined by SEC was 52.6kg/mol, with a molecular weight distribution of 1.09. The resulting polymer structure is shown below:
example 4
This example uses cis-butene diol as initiator and a phosphazene base t BuP 2 Alternating copolymerization of propylene oxide and phenyl isothiocyanate was carried out separately. The triethylboron amount in example 3 was changed to zero, and the other conditions were the same. After 72h reaction, the polymer was collected for testing.
1 H NMR test showed that the conversion of phenylisothiocyanate was 89%, the di-iso-phenylisothiocyanate and propylene oxideThe polymer content was 18% and the theoretical number-average molecular weight was 51.7 kg/mol. The number-average molecular weight determined by SEC was 42.5kg/mol, with a molecular weight distribution of 1.09. The resulting polymer structure is shown below:
example 5
The proportion of phosphazene base/lewis acid in the two-component catalyst can be flexibly adjusted, and thus unique chemical selectivity is shown. When the dosage of the phosphazene base is less than the Lewis acid, the homopolymerization of the epoxy is preferentially carried out; when the phosphazene base is used in an amount larger than the Lewis acid, the alternate copolymerization of epoxy and isothiocyanate occurs preferentially. According to the characteristic, the proportion of the phosphazene base to the Lewis acid is regulated and controlled by adding the catalyst in batches, so that the epoxy homopolymerization reaction and the copolymerization reaction can be switched to synthesize the block copolymer.
In this example, a block copolymer was synthesized by adding phosphazene base in portions and switching the homopolymerization of epoxy to the alternating copolymerization of epoxy and isothiocyanate. The specific operation is as follows:
both propylene oxide and Tetrahydrofuran (THF) were used after purification and water removal. The phenyl isothiocyanate was purified by distillation and used. In an inert atmosphere, 1 part of acetic acid and 1 part of phosphazene base t BuP 2 And a tetrahydrofuran solution (concentration: 1mol/L) containing 3 parts of triethylboron were charged into a glass reactor dried at 200 ℃ and returned to room temperature, and dissolved by adding tetrahydrofuran. And continuously adding 300 parts of phenyl isothiocyanate and 1000 parts of propylene oxide, sealing the glass reaction container, uniformly mixing by using a magnetic stirrer, and reacting for 2 hours at room temperature (20-25 ℃). Then adding 4 parts of phosphazene base t BuP 2 The reaction was continued with stirring for 10 h. In this example, the monomer concentration of phenylisothiocyanate was 2mol/L, and after completion of the polymerization, the colorless viscous product was poured from the glass reaction vessel into a large amount of methanol to be precipitated. The polymer was collected and dried in a vacuum oven heated to 80 ℃ for 12h for structural testing.
1 H NMR measurement showed the sample to be A n (AB) m The block copolymer of the type has the following structure:
example 6
In this example, the alternating copolymerization of epoxy and isothiocyanate was switched to the homopolymerization of epoxy by adding Lewis acid in batches to synthesize a block copolymer. The specific operation is as follows:
the propylene oxide and Tetrahydrofuran (THF) are used after purification and water removal. The phenyl isothiocyanate was purified by distillation and used. In an inert atmosphere, 1 part of cis-butenediol and 2 parts of phosphazene base t BuP 2 And a tetrahydrofuran solution (concentration: 1mol/L) containing 1 part of triethylboron were charged into a glass reactor dried at 200 ℃ and returned to room temperature, and dissolved by adding tetrahydrofuran. And continuously adding 300 parts of phenyl isothiocyanate and 1000 parts of propylene oxide, sealing the glass reaction container, uniformly mixing by using a magnetic stirrer, and reacting for 12 hours at room temperature (20-25 ℃). Then, a tetrahydrofuran solution (concentration: 1mol/L) containing 5 parts of triethylboron was added thereto, and the reaction was continued with stirring for 2 hours. In this example, the monomer concentration of phenylisothiocyanate was 2mol/L, and after completion of the polymerization, the colorless viscous product was poured from the glass reaction vessel into a large amount of methanol to precipitate. The polymer was collected and dried in a vacuum oven heated to 80 ℃ for 12h for structural testing.
1 H NMR measurement showed that the sample was (AB) n B m The block copolymer of the type has the following structure:
example 7
When the amount of phosphazene base is approximately equal to the amount of Lewis acid, both alternating copolymerization of epoxy and isothiocyanate and homopolymerization of epoxy can occur. In this case, the relative reactivity difference between the two monomers will directly determine the sequence structure of the main chain, so that random, gradient or tapered copolymers can be obtained by one-step reaction.
This example uses cis-butene diol as initiator and a phosphazene base t BuP 2 And a two-component catalyst combined with Lewis acid triethylboron is used for carrying out copolymerization reaction of the propylene oxide and phenyl isothiocyanate to prepare the random copolymer of the propylene oxide and the phenyl isothiocyanate by one step. The triethylboron used in example 3 was changed to 1 part, and the other conditions were the same. After 96h of reaction, the structure of the obtained polymer is shown as follows, wherein the chain links of the alternating structure and the chain links of the ether bond are randomly arranged, and the continuous units are fewer.
Example 8
In this example, the reaction was carried out for 96 hours in the same manner as in example 3 except that the amount of triethylboron used was changed to 1.2 parts. At this time, the two monomers will react in order according to the reactivity ratio difference to synthesize the gradient polymer. In the initial stage of the reaction, the epoxy homopolymerization rate is greater than the alternating copolymerization rate, so that adjacent to the initiator segment, there are significantly more ether linkage segments than alternating structural segments (y > x). Thereafter, the concentration of epoxy monomer is reduced and the rate of homopolymerization is gradually reduced while copolymerization predominates. Thus, the backbone structure of the polymer will gradually transition to ether linkages less than the alternating structural linkages (y < x).
Example 9
This example uses a more basic phosphazene base t BuP 4 Combined with triphenyl boron with stronger Lewis acidity, so as to improve the catalytic efficiency and achieve the purposes of reducing the catalyst dosage and shortening the reaction time. Replacing the metal-free acid-base pair catalyst with 0.08 part of phosphazene base t BuP 4 With 0.01 part of triphenylboron in tetrahydrofuran under other conditionsThe reaction was carried out for 20h in the same manner as in example 2. The main chain of the compound is a regular alternating sequence structure as shown in the following:
example 10
This example explores the effect of temperature on catalyst activity and polymer structure. The reaction temperature was changed to 45 ℃ and the other conditions were the same as in example 9. The reaction time is shortened to 5h, and the obtained polymer main chain keeps a regular alternating sequence structure as shown in the following:
example 11
This example explores the effect of temperature on catalyst activity and polymer structure. The reaction temperature was changed to 80 ℃ and other conditions were the same as in example 9. Reacting for 1h to obtain the polymer, wherein the main chain of the polymer is a regular alternating sequence structure as shown in the following:
example 12
In this example, bicyclic amidine and protonic acid are used to construct a metal-free acid-base pair catalyst, so as to expand the variety of the catalyst and explore the influence of nucleophilic organic base and protonic acid on the polymer structure. The catalyst was replaced with 0.08 parts of DBU and 0.01 part of 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] thiourea in tetrahydrofuran under the same conditions as in example 9. And reacting for 48h to obtain the polymer, wherein the main chain of the polymer is a regular alternating sequence structure.
Example 13
In this example, tertiary amine and protonic acid are used to construct metal-free acid-base pair catalyst, so as to expand the variety of catalyst and explore the minimum alkaline limit of organic base. The catalyst was replaced with 0.08 parts of DABCO and 0.01 parts of 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] urea in tetrahydrofuran under the same conditions as in example 12. The resulting polymer structure is shown below:
example 14
In this example, pentaerythritol was used as an initiator, and the other conditions were the same as in example 13. As shown by the structural characterization of the polymer, the four hydroxyl groups of the initiator indiscriminately initiate the copolymerization reaction of the epoxy and the isothiocyanate. The functionality of the copolymerization product is 4, the topological structure is star-shaped, and the specific structure is as follows:
example 15
This example uses terephthalyl alcohol as the initiator and solvent was replaced with toluene in order to explore the effect of solvent polarity on initiation efficiency, catalyst activity and copolymer sequence structure. Other conditions were the same as in example 2, and the resulting copolymer had a strict alternating sequence structure as shown below:
example 16
This example uses terephthalyl alcohol to initiate the copolymerization of propylene oxide and phenyl isothiocyanate to explore the feasibility of the reaction in the absence of solvent. No solvent was used, and other conditions were the same as in example 15. After 24h of reaction, the resulting copolymer had a strict alternating sequence structure as shown below:
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A catalytic method for the controllable copolymerization of epoxy and isothiocyanate is characterized by comprising the following steps: under the action of a compound containing active hydrogen as an initiator and an organic base, an acid-base pair formed by the organic base and protonic acid or the organic base and Lewis acid as a catalyst, the epoxy compound and the isothiocyanate compound carry out controllable copolymerization reaction to synthesize the heterochain polymer with the main chain containing sulfur atoms.
2. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate according to claim 1, wherein the organic base is at least one of phosphazene base, triaminophosphine, tertiary amine, amidine and guanidine; the phosphazene base is BEMP, t BuP 1 、 t BuP 2 、EtP 2 And t BuP 4 at least one of; the triaminophosphine is at least one of HMTP, HETP, TMAP and TIPAP; the tertiary amine is DABCO, PMDETA, ME 6 At least one of TREN and sparteine; the amidine is at least one of DBN and DBU; the guanidine is at least one of TBD, MTBD, TMG and PMG;
the protonic acid is a (thio) urea compound which is 1, 3-diisopropylthiourea, 1, 3-dicyclohexylurea, 1, 3-dicyclohexylthiourea, 1-cyclohexyl-3-phenylurea, 1-cyclohexyl-3- [3, 5-bis (trifluoromethyl) phenyl ] urea, 1-cyclohexyl-3-phenylthiourea, 1-cyclohexyl-3- [3, 5-bis (trifluoromethyl) phenyl ] thiourea, 1, 3-diphenylurea, 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] urea, 1, 3-diphenylthiourea, 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] thiourea and 1- (3-chlorophenyl) -3- [3, at least one of 5-dichlorophenyl urea;
the Lewis acid is an organic boron compound, and the organic boric acid is at least one of trimethyl borane, triethyl borane, diethyl methoxy borane, triisopropyl borane, tri-n-butyl borane, tri-sec-butyl borane, B-isopinocampheyl-9-boron bicyclo [3.3.1] nonane, triphenyl borane and trifluorophenyl borane.
3. The catalytic process for the controlled copolymerization of epoxy and isothiocyanate according to claim 2, wherein the organic base is t BuP 1 、 t BuP 2 、 t BuP 4 At least one of DBU and DABCO;
the protonic acid is at least one of 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] thiourea and 1, 3-bis [3, 5-bis (trifluoromethyl) phenyl ] urea;
the Lewis acid is at least one of triethylboron and triphenylboron.
4. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate according to claim 1, wherein the compound containing active hydrogen is at least one of amine, water, alcohol, phenol, carboxylic acid, thiol and amide.
5. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate according to claim 4, wherein the compound containing active hydrogen is at least one of terephthalyl alcohol, benzyl mercaptan, methoxymethyl amine, acetic acid, cis-butenediol and pentaerythritol.
6. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate, according to claim 1, wherein the epoxy compound is at least one of ethylene oxide, linear alkyl ethylene oxide with alkyl carbon number of 1 to 20, styrene oxide, cyclohexene oxide, 4-vinyl cyclohexene oxide, limonene oxide, linear alkyl glycidyl ether with alkyl carbon number of 1 to 16, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether and glycidyl methacrylate;
the isothiocyanate compound is methyl isothiocyanate, linear alkyl isothiocyanate, wherein the linear alkyl contains 2 to 20 carbon atoms, alicyclic isothiocyanate, wherein the alicyclic carbon contains 3 to 12 carbon atoms, isopropyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, benzyl isothiocyanate, phenyl isothiocyanate, o/m/p-toluene isothiocyanate, benzoyl isothiocyanate, chloroethyl isothiocyanate, cyclohexyl methyl isothiocyanate and allyl isothiocyanate.
7. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate according to claim 6, wherein the epoxy compound is at least one of ethylene oxide, propylene oxide and butylene oxide; the isothiocyanate compound is at least one of methyl isothiocyanate and phenyl isothiocyanate.
8. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate according to claim 1, wherein the temperature of the copolymerization reaction is 15-100 ℃ and the concentration of isothiocyanate is 2-10 mol/L.
9. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate according to claim 1, wherein the molar ratio of the compound containing active hydrogen, the catalyst, the epoxy compound and the isothiocyanate compound is (1-10): (0.1-10): (10-1000): (5-1000); when the catalyst is acid-base pair, the molar ratio of the organic base to the protonic acid or Lewis acid is 1: 0.1 to 15; the reaction time is 0.5-200 h.
10. The catalytic method for the controlled copolymerization of epoxy and isothiocyanate, according to claim 1, wherein the controlled copolymerization reaction can be performed in the presence or absence of a solvent, and the solvent is at least one of benzene, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, N-hexane, cyclohexane, acetone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, ethyl acetate and γ -butyrolactone.
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| CN116003771B (en) * | 2023-01-04 | 2024-10-01 | 华南理工大学 | A method for synthesizing α,β-unsaturated carboxylic acid ester functionalized polymer |
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